Process and apparatus for the reforming of naphtha hydrocarbons



Patented July 8, 1952 2,602,771 PROCESS AND APPARATUS FOR THE RE FORMTNG OF NAPHTHA HYDRO'CARBONS John C. Munday, Cranford, N. J., and Edward W. S. Nicholson, Baton Rouge, La., assignors: to Standard Oil Development Company, acorporation of Delaware Original application June 25', 1942, Serial No. 448,338. Divided and this application March 5, 1949, Serial No. 79,876

6 Claims. (Cl. 196-50) This invention relates to processes for the catalytic conversion of hydrocarbons and is more particularly concerned with improved methods of operating such processes by means of which products of superior characteristics are obtained and.v the catalyst can be usedfor substantially longer periods before requiring replacement; remanufacture or regeneration by treatment with oxygen-containing gases.

The invention is applicable to those typesof catalytic conversion processes in which the activity of the catalyst'is gradually reduced by the formation ordepositionthereon of carbonaceous contaminants such as coke. 'As examples of such processes may be mentioned catalytic cracking, catalytic reforming, catalytic dehydrogenation and catalytic aromatization whether or not carried out in'the'presence' of substantial'quantitie's of added or recirculated hydrogen or gases containing free hydrogen. The catalysts used in these processes ordinarily consist of silica, alumina, magnesia, or activated clays of the bentonitic or montmorillonitic types used alone, in

various mixtures-with each other or in combination with minor amounts, say from 1 to 50% by weight of oxides or sulfides of metals'o'f the IV, V, VI and VIII groups of the periodic system.

Processes in which catalysts of this'kindare used are characterized by alternate periods of reaction and regeneration, or reactivation of :the catalyst. The reaction portion of a cycle is continued untilthe deposition of 'carbonaceous'material on the catalyst has reduced the activity to such an extent that a product of the desired characteristics is no longer obtained or until the conversion falls below an economic level. The flow of hydrocarbon oil over the catalyst is then stopped and the catalyst is subjected to a regeneration treatment. The'nature of the carbonac'e ous deposits in these high temperature reactions does not allow a mild regenerative treatment such as solvent extraction or vaporization, as might be practiced in polymerization and Fischer synthesis reactions. In the present case a more drastic treatment such as burning the coke and carbonaceous contaminants by means of air or air'diluted' with inert gases is required, usually at relatively frequent intervals.

The length of time the catalyst can be used before it requires regeneration treatmentdepends upon a number of factors, particularly the nature of'the reaction, the character of the feed St'OCk the severity of the operating conditions, the presence or absence of substantial quantities of hydrogen during the reaction and the type of catalyst. Thus, in the-catalytic cracking of gas oilsat'temperatures between 850 and 1000 F. in

thepresence of fixed beds of catalysts consisting.

essentially of a mixture of silica and alumina the length of the reaction portion of a cyclemay be from 2-minutes to 2. hours-or more. Inthe catalytic reforming of naphthas in'the presence of catalysts consisting of a major proportion of alumina and a minor-proportion ofan oxide-of a metal oftlie VI group ofthe periodic system the length of the reaction portion of the cycle may be from l'to 3 hours or more. Whentheseprocesses are conducted under pressureandin the presence of substantial quantities of added or recirculated gasescontainingfree hydrogen the length of the reaction portion ,of-a cycle may be con-. siderably longer because the presence of free hydrogen tends to retard the deposition of coke on the catalyst. Thus incatalytic reforming in the presenceof hydrogen the reaction portion of'a'cyjcle may be from 2 to20 hoursor more.

Whenemploying finely divided catalysts in these processes-the reaction portion of the cycle is generally j considerably shorter.

We have now found that better results are'obtained in these catalyticconversion processesand that the:.necessity for-regeneration with air or other oxygen-containing gases is less frequent if the: catalyst during; the. reaction portion'of the cycle is subjected to frequent and intermitten't treatment-with hydrogen. Pure hydrogen or gases rich in freehydrogen, such as those pro.-

duced in theprocess'may be used, in such a man ner that the partial pressure of hydrogen in contact withthe catalyst is increased intermittently to a substantial degree. For example, the cata-- lystlmay be subjected to a treatment with hydrogen in the absence of-the feed stock at-intervals of from a fraction of a second to 15 minutes, 1

hour or more.- Thus, in-catalyticreiorming the hydrocarbon oil vapors may be passed over thecatalystfora period of say 1 min'ute and then hydrogen may absence of oil vaporsfor. a period of 1 minute. It is-ifoundthat by operating in this manner the rate at which coke'builds' up on the catalyst is substantially reduced" and furthermore, that the pro'ducts'obtained are greatly improvedin quality by reason of the fact that .they' are produced in the substantial absence ofcoke. I

Them'echanism by which the deposition coke is reduced and the catalyst'isreactivated. by the hydrogen treatment may be that high molecular weight polymers of unsaturated hydro-- carbons whichaccumulate-onthecatalyst-during.

be passed over the catalyst in the 3 the on-stream period are converted to volatile hydrocarbons by hydrogenation. An important element of the invention is that the elapsed time between hydrogen treatments should be relatively short, so that the heavy polymers are not allowed to stew on the catalyst and thereby become converted by dehydrogenation and polymerization to still more difiicultly volatilizable materials. Whatever the exact mechanism may be, it is an experimentally determined fact that the effectiveness of the hydrogen reactivation treatment is in indirect relationship to the onstream time between treatments. In the catalytic reforming of naphtha in the presence of hydrogen, a much greater effect is obtained when the catalyst is treated with hydrogen at intervals of a few minutes or less than at intervals of an hour or more. It should be understood, however, that such examples are given to illustrate rather than to limit the invention, since obviously the exact frequency with whichthe catalyst should be subjected to the reactivation treatment depends on a number of factors such as the nature of the feedstock, the character of the catalyst, temperature and pressure levels, feed rate, and the presence of coke-reducing gases such as hydrogen during reaction.

The intermittent type of operation accordin to the invention may be applied either to fixed bed operation in which the catalyst is stationary inside the reaction chamber or to powdered catalyst operation in which moving finely divided particles of catalyst are employed.

There are several different ways in which the intermittent operation may be carried out. One method is to maintain a circulating stream of hydrogen or hydrogen-containing gas passing through the catalyst and to inject the oil vapors into this stream for periodic short intervals. Another method is to feed hydrocarbon oil vapors and hydrogen alternately for short periods to the reaction zone. I These methods may be used when employing a fixed bed of granular or pelleted catalyst or when a mass of finely divided catalyst is maintained for a considerable period of time within the reaction zone. The second method of operation is particularly useful in carrying out reactions such as dehydrogenation in which the simultaneous presence of oil vapors and hydrogen may be undesirable because the hydrogen has an'adverse effect on the equilibrium of the reaction. A third method is to circulate finely divided catalyst continuously through reaction and hydrogen reactivation zones.

The method of carrying out the invention will be more fully understood from the following description when read with reference to the accompanying drawings which are semi-diagrammatic views in sectional elevation of two different types of apparatus in which the process may be carried out and in which Fig. 1 illustrates a type of apparatus which may be used when hydrogen is continuously passed through a bed or mass of catalyst and oil vapors are passed intermittently therethrough, or when oil vapors and hydrogen are passed alternately therethrough; and

Fig. 2 illustrates a type of apparatus which may be used when oil vapors and hydrogen are passed continuously through zones containing finely divided catalyst which is circulated between the zones.

Referring to Fig. 1, numerals I and 2 designate two reaction vessels containing a catalyst 3. Numerals 4, and 6 designate multi-way valves.

Valve 4 can have one blank side, as shown. Hydrogen is supplied from any suitable source through line I, being preheated in furnace Ia. Hydrocarbon oil is supplied from any suitable source through line 3 and may be vaporized or preheated in any suitable heating means (not shown).

When valves 4, 5 and 6 are in the position shown, hydrogen supplied through line "I passes through 4-Way valve 5 and lines 9 and I0 into reaction vessel I. No oil vapors pass through reaction vessel I because 4-way valve 4 is in the position shown. After passing through reaction vessel I wherein it reactivates the catalyst, the hydrogen flows through line I I, 4-way valve Ii, line I2 and 4-Way valve 5 and then enters reaction vessel 2 through lines I3 and I4. Meanwhile oil vapors are being supplied to reaction vessel 2 through line 8, valve 4 and line I4. A mixture of oil vapors and hydrogen thus passes through reaction vessel 2. Reaction products leave reaction vessel 2 through line I5, pass through 4-way valve 6 and then flow through line I6 to cooling, separating and fractionating equipment indicated at IT. Hydrogen recovered in the product separation system is recycled to line 7 through line I8, pump I9 and furnace 7a, or can be Withdrawn through line 20. Extraneous hydrogen may be supplied through line 30, for example, in starting up the plant.

If short periods are employed, the hydrogen withdrawn from the catalyst undergoing reactivation in I may contain a considerable quantity of hydrocarbon vapors, which it may be desirable to remove before passing the hydrogen to the other catalyst bed wherein the reaction is occurring. In this case the hydrogen stream may be passed from valve 6 through line I2, valve 22, line 2 I, valve 25 and lines 26 and IE to the product separation system I1, valves 23 and 21 being closed. The separated hydrogen is then passed through line I8, pump I9, furnace la and line I, and a portion thereof is passed to reaction vessel 2 by means of line 28, line I2, Valve 5 and lines I3 and I4, while another portion is passed to reaction vessel I through valve 5 and lines 9 and ID. If desired, the hydrogen may be purified separately from the products in equipment 29, which may take the form of an oil scrubber, or the hydrogen recovered from the separation system I! may be purified to a further degree therein, before being passed to the reaction vessels.

After oil vapors have flowed through reaction vessel 2 for a short period, say about 1 minute, valves 4, 5 and 6 are simultaneously rotated onequarter turn. This step changes the relative position of the reaction vessels I and 2, so that the catalyst in reaction vessel I is now employed for conversion of the oil and the catalyst in reaction vessel 2 is now subjected to the hydrogen reactivation treatment.

This equipment may be employed with fixed bed catalyst or with finely divided catalyst. When employing a powder of about 200-400 mesh, it is preferred to install a cyclone separator in the upper portion of each reaction vessel to recover catalyst from the gas, and to return the separated catalyst to the reaction zone through a pipe which dips below the level of powder therein, for example as shown in Fig. 2. Vapor velocities in this case should be relatively low, for example less than 2-3 feet per second in the reaction vessels, whereupon catalyst loss is relatively slight. Make-up catalyst is added as required.

After operating in this intermittent manner for a prolonged period, the catalyst 3 in reaction vessels and 2 may require an oxidative regeneration to remove coke which has'slowly been accumulating. plished in the usualway by purging the reactor of hydrocarbon gases and hydrogen and then passing air or inert gases containing regulated small quantities of oxygen through the catalyst 3 to cause combustion of the coke. Hence in order to permit continuous operation, multiple pairs of reaction vessels l and 2 may be provided so that while the catalyst in one pair is being regenerated, other pairs may be on stream.

The second modification wherein oil vapors and hydrogen are passed alternatelyin contact with the catalyst will-now be described with reference to Fig. 1. Hydrogen from line! is passed through 4-way valve 5, lines 9 and i0, and into reaction vessel l where it reactivates catalyst 3, and is withdrawn through line I l and 4-way valve 6, as before. In this modification, however, the hydrogen stream is not passed to-reaction vessel 2 but is recycled to'reaction vessel l. The hydrogen flowing through line 2| may be passed directly to the reaction vessel i through line l8, pump I9, furnace 1a and line 7, or it mayfirst bepurified inthe product separation system l'l and/or in purification equipment 29 as described above.

Meanwhile, oil vapors are being supplied to reaction vessel 2 through line 8, valve 4 and line H. Reaction products leave reaction vessel 2 through line l5, and are passed through 4-way velvet and line [6 to the cooling, separating and fractionating equipment indicated at H.

After operating in this manner for a short period, valves 4, 5 and 6 are simultaneously rotated one-quarter turn. This changes the relative positions of reaction vessels 1 and 2, so-that the catalyst in reaction vessel l is now employed for the-conversion of the oil while the catalyst in reaction vessel 2 is subjected to hydrogen reactivation treatment. It will be seen thatwhile the flow of oil and of hydrogen is continuous, the catalyst is subjected alternately to contact with oil and with hydrogen.

When the process described above is applied to endothermic reactions such as dehydrogenaion and catalytic reforming in the presence of hydrogen, there is an added advantage in that the hydrogencanbe employed as a source of. heat. Hydrogen supplied through line 1 to the catalyst being reactivated can first be heated to a high temperature in furnace 1a, whereby the catalyst following a reaction portion of the cycle can be restored to the desired reaction temperature, or evenhigher if it is desired to introduce the feed stock at a relatively low temperature in order to avoid thermal decomposition in the preheating or vaporizing coil.

Referring to Fig. 2, the apparatus illustrated is adapted for-a type of powdered catalyst operation which may be called fluid catalyst operation applied particularly to the catalytic reforming of naphtha in the presence of hydrogen. In fluid catalyst operation the finely divided catalyst is suspended or at least slightly dispersed in oil vapors or other gases, and the relative proportions of catalyst and gas and the linear velocity of ,the gas are such thatthe mixture behaves in much the same way as a fluid and may be pumped and circulated through-the .apparatus in. the same manner as afluid.

In Fig. 2, numerals 40 and 4| designate. zones Regeneration may be accomwhich are employed forreaction and-for hydrogen reactivation of the catalyst respectively. :I-Iydrogen or a hydrogen-rich stream supplied through line AZ -is-passedthrough lines 43 and 44 into the bottom of reactivation zone-M, and thence through distribution grid li into contact with the catalyst in zoneM. Hydrogenand-entrained reactivated catalyst are-removed overhead-and pass-through grids- 46 and-460L- into reaction zone 40.

The feed stock to the reaction zone is supplied through lines 41 and 48 and is passed.

through distribution grid 46a together-'withithe. hydrogen and suspended reactivated catalyst into reaction zone. The space between-reactivation zone 4! and grid 46a constitutes :amixing zone, and in some cases grid 46 is not required.

Products of the reaction in -admixture with:hy

drogen are removed overhead through-line 49 after passing through cyclone separators 50 wherein entrained catalyst particles are separated from the vapors. Catalyst recovered incyclone- 50"is returned to the reaction zonethroughpipe:

5|. To prevent by-passing of vapors through pipe 51, this pipe may extend below the-level of powder in reaction zone 40-, whereby :the .powder acts as -a seal against-the' vapors. The-product:

vaporsarepassed'to separating and :rcfining equipment (not'shown) similar-to that-described in connection with'Fig. l, Where a hydrogenrich fraction is separated for recycling to-z reactivation-zone and where the desired-'- product fraction is segregated.

Catalyst is recycled from reaction zone Ail-to reactivation zone -4l through standpipe: 52- controlled'by valve 53. It is preferred to' maintain a relatively high catalyst recirculation-rate: so that thetime of residence of the catalyst inreactionzone lfl is relatively short'before itisztransficient to allow deaeration, a fiuidizing gas-such as hydrogen or an inert gas may be introduced into the standpipe through'a. linelnot shown) in-- order to maintain the catalyst in a fluidized condition. The use of hydrogen as afiuidizing gas-has an'a'dvantage in that the catalyst withdrawn from the reaction zone is immediatelysuhjected to reactivation conditions, the relative amounts of reactivationoccurringin the standpipeandin zone 4|, depending on the relative times of contact therein.

The finely divided catalyst in reaction and reactivation zones 40 and respectively .is preferably maintained as a highly turbulent, fluidized mass'which is relatively dense ascomparedto a suspension. Atlow vapor velocities. such asa few tenthsofa foot per second to'three or four feet per second,.the.mass may be said to vhave a definite level. The mass has the appearance of a boiling liquid by reason of the passage there: throughof bubbles of vapor or of catalyst-vapor suspension, while above the level there isa sus-. pension of catalyst in vapor. At the higher velocities such as four or five feet per second, the level becomes less well defined, and it may disappearentirely at velocities of eight or ten feet per second or more-.

- Reaction zones of this type are called hindered settlers in order to distinguish :them fromv suspension reaction: zones wherein the tendency ,or

tion of the zone.

the finely divided solid to settle out of the vapors is much lesspronounced. Due to the continuous churning action in hindered settling zones, the temperature is practically constant throughout, even when endothermic or exorthermic reactions are being carried out. A further advantage is the ease with which the temperature may be controlled by the addition of hot or cold catalyst streams thereto. For example, the naphtha or other hydrocarbon feed stock may be introduced into the reactor as a relatively cool vapor or liquid, and catalyst from a regenerator or a supplementary heater may be introduced at a rela-v tively high temperature, yet the temperature in the reaction zone may vary throughout by no more than 5 or F.

The density of the catalyst mass in such hindered settling zones, and the amount of catalyst carried out with the vapors, depend on a number of factors such as the velocity of the vapors, the specific density of the catalyst, the size of the particles, the rate of catalyst addition and the free settling space in the upper por- When employing catalyst most of which is in the particle size range of from 200 to 400 mesh and has a bulk density when freely settled of about 40-70 pounds per cubic foot, the linear upward velocity through the reactor may be from 0.5 to 10.0 feet per second and the catalyst density in the reactor may be from 5 to pounds per cubic foot. In general, the higher catalyst densities are preferred since higher conversions are effected thereby.

The catalyst carry-over with the vapors leaving reaction zone may be of the order of a few thousandths of a pound per cubic foot if the flow is in the low velocity range, for example less than about 1 or 2 feet per second, and if a free settling space of about 5-15 feet is allowed above the relatively dense catalyst phase. The catalyst loading of the gases passing from the reactivation zone 4| to the reaction zone 49, however, may be considerably higher; this depends to a large extent on the catalyst flow rate to zone 4| through standpipe 52, by which the free settling space in the upper portion of zone 4| may be controlled.

The temperature in zones 40 and 4| may be maintained as desired by controlling the temperature of the streams passing thereto. For example, the temperature of the hydrogen supplied through line 42 and of the feed stock supplied through line 47 can be controlled so that zones 40 and 4| are maintained at the desired temperature levels. The temperature in zone 4| can be maintained higher than the temperature in reaction zone 48 in order to increase the efiiciency or" reactivation and also to supply heat of reac-- tion by means of hot hydrogen introduced through line 42. Another means of temperature control comprises passing a stream of fluidized catalyst through heat exchanger 54 and thence into zone 40 and/or 4|. This fluidized catalyst stream may be withdrawn from reaction zone 40 and passed through standpipes 55 and 56 to heat exchanger 54, and thence through standpipe 5? controlled by valve 58 and into the hydrogen stream passing through line 43 to reactivation zone 4|, or through standpipe 51 and the branch line controlled by valve 59 and into the feed stock stream passing through line 48 to reaction zone 40. As mentioned above, it may be necessary to supply a fluidizing gas such as an inert gas to the standpipes, for example, through lines 60, 6| and 62 in order to keep the catalyst therein in a 8. freely flowing state. The amount of fluidizing gas introduced may be relatively small, for example, sufficient to give a linear velocity of about 0.05-01 feet per second.

On continued use, there may accumulate on the catalyst a form of coke deposit which is difiicult to remove by the hydrogen treatment. Also, in some cases where catalytic activity depends on a particular state of oxidation, the catalyst cannot be maintained in a reducing atmosphere indefinitely. In such cases it is desirable to subject the catalyst to a different type of regenerative treatment, for example to an oxidative regeneration, by continuously withdrawing a portion of the catalyst from reaction zone 40 and passing it through standpipe controlled by valve 63 to regeneration zone 64. Air or other oxygen-containing gas is introduced through line 65 to the bottom of the regeneration vessel and is passed through distribution grid 66 into contact with the catalyst in regeneration zone 64. Flue gas containing products of combustion is removed overhead through line 67 after entrained catalyst is removed in the cyclone assembly 58. Separated catalyst is returned to the regeneration zone through pipe 69.

Regenerated catalyst is removed from the regeneration zone 64 through standpipe 10 controlled by valve 1|. Fluidizing gas may be introduced into standpipe 10 through lines 12, 13 and i4. Catalyst is discharged from the standpipe into the hydrogen stream introduced through line '52 and is carried thereby through lines 43 and 44 to zones 4| and 40. By this means the activity or" the catalyst in reaction zone 40 may be maintained at the desired level.

I'he specific methods employed in controlling the temperature in the reaction, reactivation and regeneration zones must be chosen with regard to the heat of reaction, the deposition of coke in a form which must be removed by burning, and the concentration of oxidizable metallic constituents in the catalyst.

II a relatively large amount of heat is liberated in regeneration zone 64 by the burning of coke and metallic constituents of the catalyst, it may be desirable to withdraw a stream of catalyst from the regeneration zone and to pass it through a cooler which may be a waste heat boiler and thence back into the regeneration zone in order to control the temperature therein. The temperature should not be allowed to rise to the deactivation temperature of the catalyst beingemployed. Suitable temperatures of regeneration, for example, may be in the range of from 900 to 1300 F.

As described in connection with Fig. 2, catalyst may be withdrawn from the reaction zone through line 55. It is generally preferred to strip the catalyst of hydrocarbons and hydrogen before passing it to an oxidative regeneration zone. For example, the catalyst may be withdrawn through line 55 from a well in the reaction zone 40 formed by a short bafile (not shown), and an inert gas such as flue gas or nitrogen may be injected into the well through a line (not shown) in order to strip the catalyst of burnable gases. Steam may sometimes be used as a stripping gas, although in the case of catalysts containing alumina, steam has a deactivating efiect and. should be avoided. If desired, a separate stripping zone operated under hindered settling conditions may be employed.

In the fluid powdered catalyst processes described above, it will be understood that catalyst flows through the reaction, reactivation, stripping and regeneration zones by reason of the fact that it is maintained as a dispersion of lesser density in upflow lines and zones than in the downflow standpipes, so that the back pressure exerted at the bottom of the low density side by the weight of powder therein is less than the pressure developed in the standpipes. The motive force which causes the powdered solid to circulate is obtained, of course, from the energy in the gases and vapors which are passed through the system. The invention in its broader phases is not to be limited to the particular systems which have been described. For example, Whereas a powdered catalyst process employing hindered settler reactors and standpipes has been described as a preferred method, the frequent reactivation of catalysts by treatment with hydrogen is equally applicable to other types of processes such as those wherein the catalyst in the reaction zone is maintained in suspension, or wherein the catalyst is circulated by means of mechanical devices such as screw pumps rather than by standpipes.

In the operation of the process in any of the ways described above, the maintenance of a pressure in the reactivation zone between say 50 and 400 or more pounds per square inch increases the effectiveness of the hydrogen during the reactivation operation. However, when employing powdered catalyst or when reactivating very frequently in fixed bed operation, it is generally preferred from a practical standpoint to maintain a hydrogen pressure of the same order of magnitude as the total pressure used in the reaction. The reaction conditions of temperature, feed rate, type of catalyst, volume of hydrogen which may accompany the oil during the reaction and so forth may be essentially the same as those ordinarily used.

It should be understood that the principal feature of the present invention is that the contact between oil and catalyst is discontinued or substantially reduced intermittently and at very short intervals and the catalyst is treated with hydrogen to remove adsorbed polymers and to efi'ect at least a partial saturation and vaporization of unsaturated materials which tend to dehydrogenate and polymerize further to form coke. By operating in this manner the rate at which coke is deposited on the catalyst is substantially reduced and hence the necessity for purging and regenerating the catalyst with air is much less frequent.

A further advantage is realized when the catalysts contain oxidizable metals or metal oxides or sulfides such as those employed in the reforming of naphthas, the aromatization and cyclization of selected hydrocarbon feedstocks in the production of aromatics, the dehydrogenation of naphthenes to aromatics and the dehydrogenation of paraflins and olefins such as butane to bu'tene and butene to butadiene. Whereas the metal oxides are used generally in a reduced or partially reduced state during the reaction period, at-the end of an oxidative regeneration period they are in an oxidized state and must either be reduced prior to use in the reaction zone or allowed to be reduced by oxidation of valuable feedstock. Additional facilities, time and reagents over those required for simply burning the coke must be provided to carry out both the oxidation and the reduction. Another important factor is that both burning the catalyst to the oxide during regeneration and subsequently reducing the oxide to a state of lower valence liberate considerable quantities of heat, which in-the case of catalysts containing more than a few percent of catalytic metal may be many times the amount of heat liberated in burning the coke contaminants. The rate at which catalysts can be regenerated or reduced without exceeding a deactivation temperature depends on the rate of heat removal, to which there is a definite practical limit. It'is evident, therefore, that the reduction in the frequency of oxidative regeneration which is achieved by the present invention is of great .practical importance in reducing the size of heat exchange equipment and the amount of waste heat, and in decreasing the length of time the catalyst is ofi-s'tream which in turn decreases the number of converters required in fixed bed operation or the size of regeneration and reduction zones required in powdered catalyst operation. In fact, it is possible when employing the present invention in some processes such as the reforming of naphtha to preheat the feedstock in the product fractionator and to vaporize the preheated liquid by'injecting into hot powdered catalyst so that a heat balance is maintained around the plant. In the case of catalysts containing high concentrations of sulfides such as those of nickel and tungsten, regeneration may require rem-anufacture; in such cases the invention has great utility since [by employing mild reaction conditions and reactivating frequently with hydrogen the coke deposition may be kept so low that regeneration is required only at very infrequent intervals. In such cases, the feedstock or the hydrogen stream may contain a sulfide such as hydrogen sulfide in order to prevent excessive desulflding' of the catalyst.

The following experiments illustrate theadlvantageous effect of intermittent operation as compared with the usual continuous operation.

Example 1 A virgin heavy naphtha derived from an East Texas crude is subjected to catalytic reforming in the presence of hydrogen at a temperature of about 911 F. under a pressure of 200 pounds per square inch, at a feed rate of 0.5 volume of liquid oil per hour per volume of catalyst, in the presencev of a catalyst comprising activated alumina and molybdenum oxide, employing 1000 cubic feet of hydrogen per barrel of oil.

In one experiment the oil and hydrogen are passed over the catalyst together in a continuous manner. In another experiment the hydrogen is passed over the catalyst continuously but the oil is passed over the catalyst in 35 second periods, thatis the oil is fed for 35 seconds and then shut 01f "for 35 seconds. Reaction is conducted ineach case for a period of 8 hours. The following table shows the important results obtained.

Contin- Interuous mittent Opera- Operation tion Aniline Point of Product, F 56 34 Coke on Catalyst, Weight Percent of Feed 0. 52 0.30

less than that deposited during the continuous operation.

Example 2 A virgin heavy naphtha derived from a West Texas crude is subjected to catalytic reforming in the presence of hydrogen at a temperature of about 960 F., under a pressure of 400 pounds per square inch, at a feed rate of 0.75 volume of liquid oil per hour per volume of catalyst, in the presence of a catalyst comprising aluminum oxide and molybdenum oxide, employing 2600 cubic feet of hydrogen recycle gas per barrel of oil.

In one experiment the oil and hydrogen are passed over the catalyst together in a continuous manner. In another experiment the hydrogen is passed over the catalyst continuously but the oil is passed over the catalyst intermittently, employing 60 minute reaction periods separated by 30 minute hydrogen reactivation periods. Reaction is conducted in each case for a period of 6 hours and the products are analyzed, the important results being shown herebelow.

Contin- Interuous mittent Opera- Operation tion Aniline Point of Product, F 58 57 Coke on Catalyst, Weight Percent on Feed." 1. 1. 04 ASTM Octane Number 80.2 80. 2

Experiments similar to those given in Example 2 are performed on a virgin heavy naphtha derived from an East Texas crude, employing equal reaction and hydrogen reactivation periods of minutes in the intermittent operation. The results obtained are shown below:

Contin- Interuous mittent Opera- Operation tion Average Temperature of Catalyst, F 940 946 Aniline Point of Product, "F 58 54 Coke on Catalyst, Weight Percent on Feed- 0. 39 0. 31

Comparing Example 2 with Example3, it will be seen that increasing the frequency of the hydrogen reactivation treatment from 60 minutes to 15 minute periods results in an advantage for the intermittent over the continuous operation in that the coke formation is reduced.

Example 4 Naphtha of the same kind as that used in the experiments of Example 1 is subjected to catalytic reforming in the presence of hydrogen at a temperature of about 911 F. under a pressure of 200 pounds per square inch, at a feed rate of 0.5 volume of liquid feed per hour per volume of catalyst, in the presence of a catalyst comprising alumina and chromia, employing 1000 cubic feet of hydrogen per barrel of oil.

In one experiment the naphtha and hydrogen are passed over the catalyst together in a continuous manner. In two other experiments the hydrogen is passd continuously and the naphtha is passed intermittently over the catalyst, em-

12 ploying equal hydroforming and hydrogen reactivation periods of 60 seconds in one experiment and 35 seconds in the other. The total time of reaction is 8 hours in each case. The more important results are shown in the following table.

Continuous Intermittent Opera- Operation tion Hydroforming Period 8 hours. 60 sec.. 35 sec. Hydrogen Reactivation Period. none 60 see- 35 sec. Aniline Point of Product, l 81 Coke on Catalyst, Weight Percent OfFeed 0.26..." 0.l2. 0.11.

These results show that under these conditions the frequent reactivation of the catalyst by the hydrogen treatment results in more than a 50% reduction in coke formation and also lowers the aniline point substantially.

Example 5 These results indicate that a decrease in the length of the reaction period below 24 seconds is not justified under the particular reaction conditions employed. At a higher rate of coke formation, a higher frequency of reactivation may, of course, be desirable. It is indicated further that the removal of coke precursors from the catalyst by the hydrogen is a relatively rapid reaction when the hydrogen treatment is applied soon after the coke precursors are deposited on the catalyst, and that a relatively short reactivation period is sufficient if the condition of frequency is met.

This invention is not limited by any theories of the mechanism of the reactions nor by any details which have been given merely for purposes of illustration but is limited only in and by the following claims in which it is intended to claim all novelty inherent in the invention.

This case is filed as a division of our application Serial No. 448,338, filed June 25, 1942, for Maintenance of Catalyst Activity in Hydrocarbon Conversion Processes, dated June 14, 1949, now U. S. Patent No. 2,472,844.

What is claimed is:

1. In a process for the reforming of naphtha hydrocarbons carried out in the presence of finely divided catalyst, the improvement which com prises passing naphtha hydrocarbons and a gas containing free hydrogen upwardly through a reforming reaction zone containing a, first turbulent dense phase bed of finely divided reforming catalyst particles which is maintained under active reforming conditions, withdrawing a controlled amount of catalyst directly from the lower portion of said first densephase bed and passin the withdrawn catalyst as a dense fluidized confined. stream into a separate reactivation zone containing a second dense phase bed of finely divided reforming catalyst particles, passing a gas containing free hydrogenv upwardly through said second dense phase bed of catalyst to effect the removal of carbonaceous deposits and reactivation of the catalyst particles therein, removing reactivated catalyst particles as, a suspension in hydrogen-containing gas overhead from said second dense phase bed, mixing hydrocarbon feed with said suspension, passing the resultant mixture into the bottom of said first. turbulent dense phase bed in said reforming reaction zone and removing reaction products overhead from said reforming reaction zone.

2. In a process for hydroforming naphthas in the presence of finely divided hydroformmg catalyst the improvement which comprises passing naphtha and a gas containing free hydrogen upwardly through a hydroiorming reaction zone containing a first turbulent dense phase bed oi finely divided hydroforming catalyst particles which is maintained under hydroforming condi tions, withdrawing controlled amounts of catalyst directly from the lower portion of said first dense phase bed and passing the withdrawn catalyst as a dense fluidized confined stream into a separate reactivation zone containing a second dense phase bed of finely divided hydroforming catalyst particles, withdrawing additional amounts of catalyst directly from the lower portion of said first dense phase bed and passing it as a dense, fluidized stream through a heat exchanger in indirect heat exchange relation to a heat exchange fluid to adjust the temperature of the catalyst particles, passing the stream of catalyst particles from the heat exchanger into said second dense phase bed in said reactivation zone, passing a gas containing free hydrogen upwardly through said second dense phase bed of catalyst to effect the removal of carbonaceous deposits and reactivation of the catalyst particles therein, removing reactivated catalyst particles as a suspension in hydrogen containing gas overhead from said second dense phase bed, mixing naphtha feed with said suspension, passing the resultant mixture into the bottom of said first turbulent dense phase bed in said hydroforming reaction zone and removing reaction products overhead from said hydroforming reaction zone.

3. In a process for hydroforming naphthas in the presence of finely divided hydroiorming catalyst, the improvement which comprises passing naphtha and a gas containing free hydrogen upwardly through a hydroforming reaction zone containing a first turbulent dense phase bed of finely divided hydroiorming catalyst particleswhich is maintained under hydroforming conditions, withdrawing controlled amounts of catalyst directly from the lower portion of said first dense phase bed and passing the withdrawn catalyst as a dense fluidized confined stream into a separate reactivation zone containing a second dense phase bed of finely divided hydroforming catalyst particles, withdrawing additional amounts of catalyst directly from the lower portion of said first dense phase bed and passing it as a dense fluidized stream through a heat exchanger in indirect heat exchange to a hot heat exchange fluid to raise the temperature of the catalyst particles to the desired level, passing a gas containing free hydrogen upwardly through said second dense phase bed of catalyst to effect the removal of carbonaceous deposits and reactivattion of the catalyst particles therein, removing reactivated catalyst particles as. a suspension in hydrogen-containing gas overhead from said second dense phase bed, mixing freshv naphtha feed with thestream of heated catalyst particles from the heat exchanger, adding this mixture tov the suspension of reactivated catalyst particles in hydrogen-containing gas and passing the resultant mixture, into the bottom of said first turbulent dense phase bed in said hydroforming reaction zone and removing reaction products over-- head from said hydroforming reaction zone.

4. In a process for the reforming of naphtha hydrocarbons carried out in the presence of finely divided reformingcatalyst, the improvement which comprises passing naphtha hydrocarbons and a gas containing free hydrogen upwardly through a reforming reaction zone containing a first turbulent dense phase bed of the catalyst and maintained under active reforming conditions, withdrawing a controlled amount of catalyst directly from the lower portion of said first dense phase bed and passing the withdrawn catalyst as a dense fluidized confined stream into a separate reactivation zone containing a second turbulent dense phase bed of catalyst, passing a gas containing free hydrogen upwardly through said second turbulent bed of catalyst to remove carbonaceous deposits and reactivate the catalyst, removing reactivated catalyst overhead from said second turbulent bed with the hydrogen containing gas as a suspension, mixing naphtha hydrocarbon feed with said suspension and passing the resultant mixture into the bottom of said first turbulent bed in said conversion zone, removin reaction products overhead from said conversion zone, removing further amounts of catalyst from said first dense phase turbulent bed in said conversion zone as a second separate dense, fluidized confined stream, passing the last mentioned stream of catalyst into a regeneration zone, introducing an oxygen-containing gas into the lower portion Of said regeneration zone to maintain the catalyst as a dense phase fluidized bed to regenerate the catalyst by burning carbonaceous deposits therefrom, withdrawing regenerated catalyst directly from the dense fluidized bed in said regeneration zone, mixing withdrawn regenerated catalyst with a hydrogen-containing gas and passing the resulting mixture into the lower portion of said separate reactivation zone.

5. An apparatus of the character described including a vessel having a bottom inlet and a top outlet, a horizontally arranged distribution grid in the lower portion of. said vessel, above said inlet, for distributing gases and solids across the entire cross sectional area of said vessel, another distribution grid spaced above said first grid and arranged horizontally in said vessel, said upper grid being provided with a standpipe for conducting fluidized solids from the zone above said upper grid to the zone above said lower grid for reactivating the solids, said solids and gases from the zone above said lower grid being returned solely through said upper grid to the zone above said upper grid as a suspension in gases, a separate pipe for withdrawing fluidized solids from the dense phase above said upper grid and a pipe for introducing reactant below said upper grid for passage upwardly through fluidized solids on said upper grid.

6. An apparatus of the character described including a vessel having a bottom inlet and a top outlet, at horizontally arranged distribution 15 rid in the lower portion of said vessel above said inlet extending over the entire cross sectional area of said vessel for distributing gases and solids across the lower portion of said vessel, another distribution grid spaced above said first grid and arranged horizontally in said vessel, said upper rid being provided with a standpipe for conducting fluidized solids from the zone above said upper grid to the zone above said lower grid for reactivating the solids, an intermediate grid arranged between said grids and above the outlet of said standpipe to provide a space below said upper grid, said solids and gases from the zone above said lower grid being passed upwardly through said intermediate grid, said space and said upper grid to the zone above said upper grid as a suspension, a separate pipe for withdrawing fluidized solids from the dense phase above said upper grid and a pipe for introducing reactant into the 16 space below said upper grid and above said intermediate grid for passage upwardly through fluidized solids on said upper grid.

JOHN C. MUNDAY. EDWARD W. S. NICHOLSON.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

1. IN A PROCESS FOR THE REFORMING OF NAPHTHA HYDROCARBONS CARRIED OUT IN THE PRESENCE OF FINELY DIVIDED CATALYST, THE IMPROVEMENT WHICH COMPRISES PASSING NAPHTHA HYDROCARBONS AND A GAS CONTAINING FREE HYDROGEN UPWARDLY THROUGH A REFORMING REACTION ZONE CONTAINING A FIRST TURBULENT DENSE PHASE BED OF FINELY DIVIDED REFORMING CATALYST PARTICLES WHICH IS MAINTAINED UNDER ACTIVE REFORMING CONDITIONS, WITHDRAWING A CONTROLLED AMOUNT OF CATALYST DIRECTLY FROM THE LOWER PORTION OF SAID FIRST DENSE PHASE BED AND PASSING THE WITHDRAWN CATALYST AS A DENSE FLUIDIZED CONFINED STREAM INTO A SEPARATE REACTIVATION ZONE CONTAINING A SECOND DENSE PHASE BED OF FINELY DIVIDED REFORMING CATALYST PARTICLES, PASSING A GAS CONTAINING FREE HYDROGEN UPWARDLY THROUGH SAID SECOND DENSE PHASE BED OF CATALYST TO EFFECT THE REMOVAL OF CARBONACEOUS DEPOSITS AND REACTIVATION OF THE CATALYST PARTICLES THEREIN, REMOVING REACTIVATED CATALYST PARTICLES AS A SUSPENSION IN HYDROGEN-CONTAINING GAS OVERHEAD FROM SAID SECOND DENSE PHASE BED, MIXING HYDROCARBON FEED WITH SAID SUSPENSION, PASSING THE RESULTANT MIXTURE INTO THE BOTTOM OF SAID FIRST TURBULENT DENSE PHASE BED IN SAID REFORMING REACTION ZONE AND REMOVING REACTION PRODUCTS OVERHEAD FROM SAID REFORMING REACTION ZONE. 